CN108341922B - Preparation method and application of low-Tg polyurethane acrylate prepolymer - Google Patents
Preparation method and application of low-Tg polyurethane acrylate prepolymer Download PDFInfo
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
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Abstract
The invention provides a preparation method and application of a low Tg polyurethane acrylate prepolymer. The invention takes polyisobutylene diol, aliphatic diisocyanate or aromatic diisocyanate, acrylic hydroxyl ester, polymerization inhibitor and catalyst as raw materials. The preparation of the low Tg polyurethane acrylate prepolymer is completed through 2 steps of synthesis. The preparation method comprises the following steps: stirring and mixing polyisobutylene diol, aliphatic diisocyanate or aromatic diisocyanate and a catalyst uniformly, heating and reacting to the theoretical endpoint of NCO%, adding hydroxyl acrylate, the catalyst and a polymerization inhibitor, stirring and heating to react until the NCO% is less than or equal to 0.15%. The low Tg polyurethane acrylate prepolymer provided by the invention has Tg lower than-75 ℃, has super-good flexibility, and can be used as main resin of super-flexible low-temperature-resistant optical fiber coatings.
Description
Technical Field
The invention belongs to the technical field of polymer synthesis, and particularly relates to a preparation method and application of a low-Tg polyurethane acrylate prepolymer.
Background
With the improvement of living standard of people, people have more and more strong calls for environmental protection, and the traditional solvent-based coating volatilizes organic solvent from a coating film, thus not only causing harm to human bodies, but also causing pollution to the environment. The radiation curing coating is a coating which can form a solid coating film by crosslinking and polymerizing liquid prepolymer under the action of ultraviolet light (UV), visible light or electron beams. The radiation curing technology has the characteristics of '5E': high efficiency (efficiency), wide adaptability (adaptability), economy (Economic), Energy conservation (Energy Saving) and Environmental friendliness (Environmental Friendly).
The ultraviolet curing (UV) coating develops very rapidly since commercialization has been achieved, and the application fields are also developed from the initial wood coating to the industrial fields of paper, plastics, glass, medical instruments, optical fibers and the like. Ultraviolet (UV) curable coatings vary from application to application, but are essentially composed of a prepolymer, a reactive diluent, a photoinitiator, and an auxiliary agent. The main types of prepolymers are unsaturated polyesters, polyester acrylates, polyether acrylates, polyurethane acrylates, which are the main components of uv-curable coatings, whose properties essentially determine the main properties of the coating.
However, the Tg of the prepolymer currently used for Ultraviolet (UV) curable coatings is relatively high, so that the flexibility and low temperature resistance of the optical fiber coating cured film using the prepolymer as a main resin cannot meet the use requirements of adding a special environment.
Disclosure of Invention
In view of the deficiencies of the prior art, it is an object of the present invention to provide a low Tg urethane acrylate prepolymer and its use.
The invention provides a low Tg urethane acrylate prepolymer by using polyisobutylene diol as the flexible chain end of urethane acrylate. Because two symmetrical methyl groups on quaternary carbon atoms in the polyisobutylene diol reduce internal rotation barriers in a main chain and improve flexibility, the obtained polyurethane acrylate prepolymer has lower Tg. And the optical fiber coating curing film taking the optical fiber coating curing film as the main body resin has better flexibility and excellent low-temperature resistance.
The purpose of the invention is realized by the following technical scheme:
in a first aspect, the present invention provides a method for preparing a low Tg urethane acrylate prepolymer, comprising the steps of:
s1, adding polyisobutylene diol, diisocyanate and a catalyst at room temperature, heating and stirring, reacting until the NCO% reaches the theoretical midpoint, and stopping the reaction to obtain an intermediate mixture;
s2, adding hydroxyl acrylate, a catalyst and a polymerization inhibitor into the intermediate mixture, heating and stirring, reacting until NCO% is less than or equal to 0.15%, and stopping the reaction to obtain the prepolymer;
wherein the charging molar ratio of the polyisobutene diol to the diisocyanate to the hydroxyl acrylate is (1.0-5.0): (2.0-8.0): (2.0-8.0);
in the steps S1 and S2, the using amount of the catalyst is 0.01-0.1% of the total mass of the prepolymer;
the amount of the polymerization inhibitor is 0.1-2% of the total mass of the prepolymer.
Preferably, the charging molar ratio of the polyisobutene glycol to the diisocyanate to the hydroxyl acrylate is 2:3: 2.
Preferably, the molar ratio of NCO of the intermediate mixture to OH of the hydroxyl acrylate is (0.8-1.05): (0.8-1.05) feeding. More preferably, the intermediate mixture has a molar NCO to hydroxy acrylate OH ratio of 1: 1.
Preferably, the molecular weight of the polyisobutene diol is 1000-7000. More preferably 2000.
Preferably, the diisocyanate is selected from at least one of aliphatic diisocyanates and aromatic diisocyanates. Specifically, the diisocyanate is selected from one or more of 1, 6-hexane diisocyanate, isophorone diisocyanate, methylene bis (4-cyclohexyl isocyanate), 2, 4-trimethyl hexamethylene diisocyanate, 2, 5-bis (isocyanatomethyl) -bicyclo [2.2.1] heptane, 2, 6-bis (isocyanatomethyl) -bicyclo [2.2.1] heptane, m-phenylene diisocyanate, p-phenylene diisocyanate, 3 '-dimethyl-4, 4' -diphenylmethane diisocyanate, 3 '-dimethylphenylene diisocyanate and 4, 4' -biphenyl diisocyanate. More preferably, the diisocyanate is isophorone diisocyanate.
Preferably, the hydroxyl acrylate is 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 1, 4-butanediol mono (meth) acrylate, 1, 6-hexanediol mono (meth) acrylate or neopentyl glycol mono (meth) acrylate.
More preferably, the hydroxy acrylate is hydroxyethyl acrylate, 2-hydroxyethyl (meth) acrylate or 2-hydroxypropyl (meth) acrylate.
Preferably, the catalyst is dibutyltin dilaurate, N-dimethylbenzylamine, N-dimethylcyclohexylamine, N' -dimethylpyridine, or tetraisooctyl titanate.
More preferably, the catalyst is dibutyltin dilaurate, and the amount of the catalyst is 0.025-0.1% of the total mass of the prepolymer.
Preferably, the polymerization inhibitor is tert-butyl hydroquinone, p-hydroxyanisole, hydroquinone or o-methyl hydroquinone.
More preferably, the polymerization inhibitor is p-hydroxyanisole, and the dosage of the polymerization inhibitor is 0.5-1% of the total mass of the prepolymer. A polymerization inhibitor content of less than 0.5% results in resin gelation, and a content of more than 1% affects resin quality and lowers resin properties.
Preferably, in step S1, the heating temperature is 30 ℃ to 70 ℃; in step S2, the heating temperature is 70-90 ℃.
In a second aspect, the present invention provides a low Tg urethane acrylate prepolymer obtained according to the above preparation method, said prepolymer having a Tg of less than-75 ℃.
The low Tg urethane acrylate prepolymer is di-or multi-functional. The low Tg polyurethane acrylate prepolymer has super-good flexibility and can be used as a main resin of super-flexible low-temperature-resistant optical fiber coatings.
In a third aspect, the invention provides an application of the urethane acrylate prepolymer in preparation of a main resin of an ultra-flexible low-temperature-resistant optical fiber coating.
Compared with the prior art, the invention has the following beneficial effects:
the invention provides a low Tg urethane acrylate prepolymer by using polyisobutylene diol as the flexible chain end of urethane acrylate. Because two symmetrical methyl groups on quaternary carbon atoms in the polyisobutylene diol reduce internal rotation barriers in a main chain and improve flexibility, the obtained polyurethane acrylate prepolymer has lower Tg. The optical fiber coating cured film using the epoxy resin as the main body resin has good flexibility and excellent low-temperature resistance.
The low Tg polyurethane acrylate prepolymer provided by the invention has Tg lower than-75 ℃, has super-good flexibility, and can be used as main resin of super-flexible low-temperature-resistant optical fiber coatings.
Detailed Description
The present invention will be described in detail with reference to specific examples. The following examples will assist those skilled in the art to further understand the present invention, but do not limit the scope of the present invention. After reading the description of the present invention, one skilled in the art can make several variations and modifications without departing from the spirit of the present invention, and such equivalent variations and modifications also fall within the scope of the present invention as defined in the appended claims.
Example 1
This example relates to a method for preparing a low Tg urethane acrylate prepolymer, comprising:
26.7g, 0.12mol of isophorone diisocyanate and 0.040g of dibutyltin dilaurate are respectively added into a 250ml reaction bottle, 120.0g and 0.06mol of polyisobutylene diol 2000 are dropwise added under the stirring state, the reaction system is maintained at 40-50 ℃ by oil bath heating until the NCO content in the system is close to the theoretical terminal point, 0.12mol of hydroxyethyl acrylate, 0.803g of p-hydroxyanisole and 0.040g of dibutyltin dilaurate are added, the temperature of the reaction system is adjusted to 70-90 ℃, and the reaction is ended when the NCO content is less than 0.15%.
Example 2
This example relates to a method for preparing a low Tg urethane acrylate prepolymer, comprising:
adding 17.8g, 0.08mol of isophorone diisocyanate and 0.036g of dibutyltin dilaurate into a 250ml reaction bottle respectively, dropwise adding 120.0g and 0.04mol of polyisobutylene diol 3000 under a stirring state, heating in an oil bath to maintain the reaction system at 40-50 ℃ until the NCO content in the system is close to the theoretical terminal point, adding 0.08mol of hydroxyethyl acrylate, 0.735g of p-hydroxyanisole and 0.036g of dibutyltin dilaurate, adjusting the temperature of the reaction system to 70-90 ℃, and finishing the reaction when the NCO content is less than 0.15%.
Example 3
This example relates to a method for preparing a low Tg urethane acrylate prepolymer, comprising:
respectively adding 20.0g, 0.09mol of isophorone diisocyanate and 0.037g of dibutyltin dilaurate into a 250ml reaction bottle, dropwise adding 120.0g and 0.06mol of polyisobutylene diol 2000 under a stirring state, heating in an oil bath to maintain the reaction system at 40-50 ℃ until the NCO content in the system is close to the theoretical terminal point, adding 0.06mol of hydroxyethyl acrylate, 0.735g of p-hydroxyanisole and 0.037g of dibutyltin dilaurate, adjusting the temperature of the reaction system to 70-90 ℃, and finishing the reaction when the NCO content is less than 0.15%.
Example 4
This example relates to a method for preparing a low Tg urethane acrylate prepolymer, comprising:
respectively adding 13.3g, 0.06mol of isophorone diisocyanate and 0.034g of dibutyltin dilaurate into a 250ml reaction bottle, dropwise adding 120.0g and 0.04mol of polyisobutylene diol 3000 under a stirring state, heating in an oil bath to maintain the reaction system at 40-50 ℃ until the NCO content in the system is close to a theoretical terminal point, adding 0.04mol of hydroxyethyl acrylate, 0.690g of p-hydroxyanisole and 0.034g of dibutyltin dilaurate, adjusting the temperature of the reaction system to 70-90 ℃, and finishing the reaction when the NCO content is less than 0.15%.
Example 5
This example relates to a method for preparing a low Tg urethane acrylate prepolymer, comprising:
adding 17.8g, 0.08mol of isophorone diisocyanate and 0.036g of dibutyltin dilaurate into a 250ml reaction bottle respectively, dropwise adding 120.0g and 0.06mol of polyisobutylene diol 2000 under a stirring state, heating in an oil bath to maintain the reaction system at 40-50 ℃ until the NCO content in the system is close to a theoretical terminal point, adding 0.04mol of hydroxyethyl acrylate, 0.712g of p-hydroxyanisole and 0.036g of dibutyltin dilaurate, adjusting the temperature of the reaction system to 70-90 ℃, and finishing the reaction when the NCO content is less than 0.15%.
Example 6
This example relates to a method for preparing a low Tg urethane acrylate prepolymer, comprising:
respectively adding 13.3g, 0.06mol of isophorone diisocyanate and 0.038g of dibutyltin dilaurate into a 250ml reaction bottle, dropwise adding 135.0g and 0.045mol of polyisobutylene diol 3000 under a stirring state, heating in an oil bath to maintain the reaction system at 40-50 ℃ until the NCO content in the system is close to a theoretical terminal point, adding 0.03mol of hydroxyethyl acrylate, 0.759g of p-hydroxyanisole and 0.038g of dibutyltin dilaurate, adjusting the temperature of the reaction system to 70-90 ℃, and finishing the reaction when the NCO content is less than 0.15%.
Example 7
This example relates to a method for preparing a low Tg urethane acrylate prepolymer, comprising:
respectively adding 20.2g, 0.12mol of 1, 6-hexane diisocyanate and 0.1475g N, N-dimethylbenzylamine into a 250ml reaction bottle, dropwise adding 560g and 0.08mol of polyisobutene diol 7000 into the reaction bottle under a stirring state, and heating the reaction bottle in an oil bath to maintain the temperature of the reaction system at 30 ℃ until the NCO content in the reaction system approaches to the theoretical terminal point to obtain an intermediate mixture; the intermediate mixture had an NCO molar amount of 0.08mol, and 0.08mol of 2-hydroxypropyl (meth) acrylate and 1.18g of t-butylhydroquinone were added together with 0.1475g N, N-dimethylbenzylamine, while the reaction system temperature was adjusted to 70 ℃ to terminate the reaction until the NCO content was less than 0.15%.
Example 8
This example relates to a method for preparing a low Tg urethane acrylate prepolymer, comprising:
respectively adding 16.04g, 0.09mol of 2, 5-bis (isocyanatomethyl) -bicyclo [2.2.1] heptane and 0.081g of tetraisooctyl titanate into a 250ml reaction bottle, dropwise adding 300g and 0.06mol of polyisobutene glycol 5000 under the stirring state, heating in an oil bath to maintain the reaction system at 70 ℃ until the NCO content in the system approaches the theoretical terminal point, and obtaining an intermediate mixture; the intermediate mixture had an NCO molar amount of 0.06mol, and 0.06mol of 1, 4-butanediol mono (meth) acrylate, 0.646g of o-methyl hydroquinone and 0.081g of tetraisooctyl titanate were added while the temperature of the reaction system was adjusted to 90 ℃ to terminate the reaction until the NCO content was less than 0.15%.
Comparative example 1
The present comparative example relates to a method of preparing a low Tg urethane acrylate prepolymer comprising:
respectively adding 13.3g, 0.06mol of isophorone diisocyanate and 0.034g of dibutyltin dilaurate into a 250ml reaction bottle, dropwise adding 2000-3000 mol of polyethylene glycol under stirring, heating in an oil bath to maintain the reaction system at 40-50 ℃ until the NCO content in the system is close to the theoretical terminal point, adding 0.04mol of hydroxyethyl acrylate, 0.690g of p-hydroxyanisole and 0.034g of dibutyltin dilaurate, adjusting the temperature of the reaction system to 70-90 ℃, and finishing the reaction when the NCO content is less than 0.15%.
Comparative example 2
This comparative example relates to a process for preparing a low Tg urethane acrylate prepolymer, which is substantially identical to example 1 except that: 120.0g of 0.06mol of the bishydroxypolysiloxane 2000 were added dropwise with stirring.
Comparative example 3
This comparative example relates to a process for preparing a low Tg urethane acrylate prepolymer, which is substantially identical to example 1 except that: and dropping 120.0g and 0.06mol of 2000-3000 of polyisoprene glycol under the stirring state.
Application testing
The contents of the coating compositions of the examples and comparative examples are shown in table 1 below:
TABLE 1
Coating a coating on the surface of glass serving as a base material by using a coating device, wherein the coating thickness is 0.1-0.25 mm, and the energy is 500mJ/cm through UV curing2。
The cured films prepared in examples 1 to 8 and comparative example were subjected to performance testing, and the viscosity of the coating, the curing degree, refractive index, tensile strength, elongation at break, Tg, high and low temperature performance, and the like of the cured films were measured.
The cured film test results are shown in table 2 below:
TABLE 2
The method corresponding to the performance detection item comprises the following steps:
viscosity of
Measurement was carried out using a rotational viscometer model NDJ-8S from Shanghai instruments Ltd
Degree of cure
And detecting the double bond conversion rate of the cured film by using an infrared spectrometer.
Refractive index of three
Measurement Using WAP Abbe refractometer manufactured by Shanghai precision instruments Ltd
Tensile strength and elongation at break
The test is carried out by adopting an MTS-E43 universal electronic tester.
Tg of five
The measurement was carried out by using a dynamic thermomechanical analyzer model DMA 8000 manufactured by Perkinelmer.
High and low temperature test
In the low temperature resistance test, the test is carried out in a refrigerator by adopting a gradual cooling method. The coating cured films prepared in the examples and the comparative examples are put into a freezer, the temperature is reduced from 2 ℃ to 10 ℃ per hour, and the phenomenon is observed and found as follows: the coating surface of the coating prepared by the comparative example becomes wrinkled and yellow when the temperature of the coating cured film is below 36 ℃. The coatings formulated in the examples cured the film to-70 c with no change.
In the high temperature resistance test, a gradual temperature rise method is adopted in an oven for testing. The cured films of the coatings prepared in the examples and comparative examples were placed in an oven and the temperature was increased from 25 ℃ to 10 ℃ per hour, and observed to be: the cured films of the coatings prepared in the examples and comparative examples started to yellow and bubble on the coating surface when the temperature reached 120 ℃.
As can be seen from table 2 above, from the results of example 4 and comparative example 1, and example 1 and comparative example 2, it can be seen that the addition of polyisobutylene diol, compared to polyethylene glycol, double hydroxyl-terminated polysiloxane, reduces the internal rotation barrier in the main chain and increases the flexibility due to the two symmetrical methyl groups on the quaternary carbon atom in polyisobutylene diol, and thus the resulting urethane acrylate prepolymer has a lower Tg and the cured film of the coating formulated has a lower Tg and low temperature resistance; example 1 compared with comparative example 3, comparative example 3 added other compounds having two symmetrical methyl groups, but had poor flexibility due to the higher viscosity and higher Tg point of the polyurethane acrylate prepolymer prepared from polyisoprene glycol.
Therefore, the optical fiber coating cured film mainly prepared from the polyurethane acrylate prepolymer has low Tg and outstanding low-temperature resistance, and is suitable for being used in environments with high requirements.
The foregoing description of specific embodiments of the present invention has been presented. It is to be understood that the present invention is not limited to the specific embodiments described above, and that various changes and modifications may be made by one skilled in the art within the scope of the appended claims without departing from the spirit of the invention.
Claims (10)
1. A preparation method of a low Tg polyurethane acrylate prepolymer is characterized by comprising the following steps:
s1, adding polyisobutylene diol, diisocyanate and a catalyst at room temperature, heating and stirring, reacting until the NCO% reaches a theoretical end point, and stopping the reaction to obtain an intermediate mixture;
s2, adding hydroxyl acrylate, a catalyst and a polymerization inhibitor into the intermediate mixture, heating and stirring, reacting until NCO% is less than or equal to 0.15%, and stopping the reaction to obtain the prepolymer;
wherein the charging molar ratio of the polyisobutene diol to the diisocyanate to the hydroxyl acrylate is (1.0-5.0): (2.0-8.0): (2.0-8.0);
in the steps S1 and S2, the using amount of the catalyst is 0.01-0.1% of the total mass of the prepolymer;
the using amount of the polymerization inhibitor is 0.1-2% of the total mass of the prepolymer;
wherein the prepolymer has a Tg of less than-75 ℃.
2. The method for preparing a low Tg urethane acrylate prepolymer according to claim 1, wherein the intermediate mixture and the hydroxy acrylate are in a molar ratio of NCO of the intermediate mixture to OH of the hydroxy acrylate of (0.8-1.05): (0.8-1.05) feeding.
3. The method for preparing a low Tg urethane acrylate prepolymer according to claim 1 wherein the number average molecular weight of the polyisobutylene diol is 1000 to 7000.
4. The method of claim 1, wherein the diisocyanate is at least one selected from the group consisting of aliphatic diisocyanate and aromatic diisocyanate.
5. The method of claim 1, wherein the hydroxy acrylate is 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 1, 4-butanediol mono (meth) acrylate, 1, 6-hexanediol mono (meth) acrylate, or neopentyl glycol mono (meth) acrylate.
6. The method of preparing a low Tg urethane acrylate prepolymer according to claim 1 wherein said catalyst is dibutyltin dilaurate, N-dimethylbenzylamine, N-dimethylcyclohexylamine, N' -lutidine, or tetraisooctyl titanate.
7. The method of claim 1, wherein the polymerization inhibitor is tert-butylhydroquinone, p-hydroxyanisole, hydroquinone or o-methylhydroquinone.
8. The method for preparing a low Tg urethane acrylate prepolymer according to claim 1, wherein the heating temperature is 30 ℃ to 70 ℃ in step S1; in step S2, the heating temperature is 70-90 ℃.
9. A low Tg urethane acrylate prepolymer, wherein said prepolymer is obtained according to the method of any one of claims 1 to 8, said prepolymer having a Tg of less than-75 ℃.
10. Use of the low Tg urethane acrylate prepolymer according to claim 9 in the preparation of a host resin for ultra-flexible low temperature resistant optical fiber coatings.
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| CN114525077A (en) * | 2022-01-26 | 2022-05-24 | 尚宁智感(北京)科技有限公司 | Photocuring low-glass-transition-temperature optical fiber internal coating formula and preparation method thereof |
| CN114561155A (en) * | 2022-03-08 | 2022-05-31 | 上海回天新材料有限公司 | UV (ultraviolet) buffer adhesive and preparation method thereof |
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| CN103833956A (en) * | 2014-03-03 | 2014-06-04 | 黎明化工研究设计院有限责任公司 | High molecular weight urethane acrylate resin and preparation method thereof |
| CN104892890A (en) * | 2014-09-30 | 2015-09-09 | 深圳市浩力新材料技术有限公司 | Ultra-flexible polyurethane acrylate resin and liquid-state optical adhesive composition thereof |
| CN105925238A (en) * | 2016-06-28 | 2016-09-07 | 烟台信友新材料股份有限公司 | UV-curing adhesive with low Tg point and high permeability and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103833956A (en) * | 2014-03-03 | 2014-06-04 | 黎明化工研究设计院有限责任公司 | High molecular weight urethane acrylate resin and preparation method thereof |
| CN104892890A (en) * | 2014-09-30 | 2015-09-09 | 深圳市浩力新材料技术有限公司 | Ultra-flexible polyurethane acrylate resin and liquid-state optical adhesive composition thereof |
| CN105925238A (en) * | 2016-06-28 | 2016-09-07 | 烟台信友新材料股份有限公司 | UV-curing adhesive with low Tg point and high permeability and preparation method thereof |
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